The synthesis of a p-toluidine/formal dehyde (PTF) resin was performed, and the effects of the molar ratio of the individual monomers and the polymerization conditions on the structure of the PTF resin were studied. Fourier transform infrared and C-13-NMR spectra were used to characterize the PTF. Wide-angle X-ray diffraction patterns revealed the crystalline structures of various PTFs. Polarized optical microscopy revealed that the molar ratio of the monomers had a strong effect on the crystalline morphologies. A longer polymerization time turned out a polymer with a higher intrinsic viscosity and molecular weight, which led to differences in the proton conductivity. All of the PTFs showed a higher proton conductivity than a commercial Nafion membrane at 90-100 degrees C and 0% relative humidity. The proton conductivity of the PTF series could be improved by sulfonation with sulfuric acid and could be maintained after blending with polyurethane. Pure methanol could be used as a fuel source because of the insolubility and nonwetting properties of PTF in methanol to increase the output current density for a PTF membrane electrode assembly. (C) 2007 Wiley Periodicals, Inc.